Line pattern collapse mitigation through gap-fill material application

ABSTRACT

Disclosed is a method and apparatus for mitigation of photoresist line pattern collapse in a photolithography process by applying a gap-fill material treatment after the post-development line pattern rinse step. The gap-fill material dries into a solid layer filling the inter-line spaces of the line pattern, thereby preventing line pattern collapse due to capillary forces during the post-rinse line pattern drying step. Once dried, the gap-fill material is depolymerized, volatilized, and removed from the line pattern by heating, illumination with ultraviolet light, by application of a catalyst chemistry, or by plasma etching.

CROSS REFERENCE TO RELATED APPLICATIONS

This application is based on and claims the benefit of and priority toU.S. Provisional Patent Application No. 61/306,512, entitled “LINEPATTERN COLLAPSE MITIGATION THROUGH GAP-FILL MATERIAL APPLICATION” (Ref.No. CT-095PRO), filed on Feb. 21, 2010, and co-pending U.S. patentapplication Ser. No. 13/031,112, entitled “LINE PATTERN COLLAPSEMITIGATION THROUGH GAP-FILL MATERIAL APPLICATION” (Ref. No. CT-095),filed on Feb. 18, 2011, the entire contents of all of which are hereinincorporated by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method and apparatus for mitigationof photoresist line pattern collapse in a photolithography process byapplying a gap-fill material treatment after the post-development linepattern rinse step, and subsequent removal thereof to expose the linepattern.

2. Description of Related Art

Photolithography processes for manufacturing semiconductor devices,liquid crystal displays (LCDs), and photovoltaics generally coat a layerof radiation-sensitive material, such as photoresist, on a substrate,expose the radiation-sensitive material coating to light to impart alatent image line pattern, and develop the exposed radiation-sensitivematerial coating to transform the latent image line pattern into a finalimage line pattern having masked and unmasked areas. Such a series ofprocessing stages is typically carried out in a coating/developingsystem.

Feature sizes of semiconductor device circuits have been scaled to lessthan 0.1 micron. Typically, the pattern wiring that interconnectsindividual device circuits is formed with sub-micron line widths. In thepost-development phase of a photolithography process, once a photoresistline pattern has been already formed, a deionized water rinse step isused to remove the developer from and clean the developed line pattern.Following the rinse step, the photoresist line pattern and substrate aredried so the substrate can be transported to the next processing toolfor the next processing step. During the drying step, capillary forcesarise at the interfaces between the deionized water or other rinseliquid, ambient air, and the photoresist material. The tighter thephotoresist line pattern (i.e. the smaller the line pattern pitch), thelarger the capillary forces become, and in some cases these forces canovercome the mechanical strength of the photoresist line pattern itself,leading to line pattern collapse. Once collapsed, the photoresist linepattern does not anymore represent an exact image of the image linepattern applied to the photoresist during the exposure step, leading tolower device yields, etc.

A number of ways have been used to mitigate line pattern collapsegenerally involving reducing the surface tension of the rinse liquid incontact with the photoresist. For example, a surfactant can be added tothe rinse liquid (e.g. deionized water) to reduce the surface tension,and hence capillary forces acting upon the photoresist line patternduring the drying step. Another approach involves adding a reactiveadditive to the rinse liquid (e.g. deionized water), to react with thepolymeric photoresist material, with the effect of modifying the surfaceenergy of the photoresist and hence lowering the contact angle (i.e.wetting angle) and capillary forces. However, these methods may havelimitations. For example, surfactants compatible with thephotolithography process and materials can only reduce the surfacetension a certain amount, and a larger reduction may be necessary toovercome the increase of capillary forces due to photoresist linepattern pitch reduction in newer generations of semiconductor devices.Therefore, there exists a need for a method of mitigating photoresistline pattern collapse without the above shortcomings, and which will beeffective for next generations of semiconductor.

SUMMARY OF THE INVENTION

The present invention relates to a method and apparatus for mitigationof photoresist line pattern collapse in a photolithography process byapplying a gap-fill material treatment after the post-development linepattern rinse step, and subsequent removal thereof to expose the linepattern.

According to an embodiment, a method of patterning a substrate isprovided, comprising: forming a layer of radiation-sensitive material onthe substrate; performing a patterned exposure of the layer ofradiation-sensitive material; performing a post-exposure bake of thelayer of radiation-sensitive material; developing the layer ofradiation-sensitive material to form a radiation sensitive materialpattern; rinsing the radiation-sensitive material pattern with a rinseliquid; dispensing gap-fill treatment liquid on the radiation-sensitivematerial pattern to displace the rinse liquid; and spinning thesubstrate to remove excess gap-fill treatment liquid and allow theremaining gap-fill treatment liquid to dry, thereby forming a gap-fillmaterial layer which prevents collapse of the radiation-sensitivematerial pattern. These steps are followed by removing the gap-fillmaterial layer from the radiation-sensitive material pattern.

According to further embodiments of the invention, the gap-fill materialis depolymerized, volatilized, and removed from the line pattern byheating, illumination with electromagnetic (e.g. ultraviolet light orlaser) radiation, by application of a catalyst chemistry, by plasmaetching, or a combination of two or more thereof.

According to yet further embodiments of the invention, the gap-filltreatment liquid can comprise a polymer compound that depolymerizes intovolatile compounds on exposure to at least one depolymerizing agent fromthe group consisting of heat, electromagnetic radiation, a catalyst, ora plasma in an etch processing tool.

According to yet further embodiments of the invention, the gap-filltreatment liquid can comprise at least one polymer compound from thegroup consisting of poly(vinyl alcohol), poly(acrylamide),poly(phtalaldehyde), poly(succinaldehyde), poly(allyl alcohol),poly(glyoxylic acid), poly(methyl glyoxylic acid), poly(ethyl glyoxylicacid), poly(methyl glyoxylate), poly(ethyl glyoxylate), andpoly(aspartic acid). Furthermore, the gap-fill treatment liquid cancomprise at least one polymer salt of the poly(methyl glyoxylic acid)and/or poly(ethyl glyoxylic acid), such as ammonium and sodium polymersalts thereof.

BRIEF DESCRIPTION OF THE DRAWINGS

A more complete appreciation of the invention and many of the attendantadvantages thereof will become readily apparent with reference to thefollowing detailed description, particularly when considered inconjunction with the accompanying drawings, in which:

FIG. 1 is a plan view showing the general structure of acoating/developing system used to process substrates in accordance withan embodiment of the invention.

FIG. 2 is a front view of the coating/developing system in FIG. 1.

FIG. 3 is a rear view of the coating/developing system in FIG. 1.

FIG. 4 is schematic of an embodiment of a method for mitigation ofphotoresist line pattern collapse by the application of gap-fillmaterial.

FIG. 5 is a flowchart of an embodiment of a method for mitigation ofphotoresist line pattern collapse by the application of gap-fillmaterial.

FIG. 6 shows a table of polymer compounds useful as gap-fill materialsfor photoresist line pattern collapse mitigation.

FIG. 7 is schematic of an exemplary embodiment of a developing devicecapable of performing, in part, the method outlined in the flowchart ofFIG. 5.

FIG. 8 is a schematic of an exemplary embodiment of a heating device inaccordance with an embodiment of the invention.

FIG. 9 is a schematic of an exemplary embodiment of an illuminationdevice in accordance with an embodiment of the invention.

DETAILED DESCRIPTION OF EXEMPLARY EMBODIMENTS

In the following description, in order to facilitate a thoroughunderstanding of the invention and for purposes of explanation and notlimitation, specific details are set forth, such as particulargeometries of a lithography, coater/developer, and gap-fill treatmentsystem, and descriptions of various components and processes. However,it should be understood that the invention may be practiced in otherembodiments that depart from these specific details.

In the description to follow, the terms radiation-sensitive material andphotoresist may be used interchangeably, photoresist being only one ofmany suitable radiation-sensitive materials for use in photolithography.Similarly, hereinafter the term substrate, which represents theworkpiece being processed, may be used interchangeably with terms suchas semiconductor wafer, LCD panel, photovoltaic device panel, etc., theprocessing of all of which falls within the scope of the claimedinvention.

An exemplary coating/developing system 100, as shown in FIG. 1, may beconstituted to integrally connect a cassette station 102, whichtransports a cassette typically holding 25 substrates, such assemiconductor wafers 104, for example, into the coating/developingsystem 100 from outside and which transports a wafer 104 to the cassette106; an inspection station 108, which performs a predeterminedinspection on the wafer 104; a processing station 110 with a pluralityof types of processing devices disposed in stages to performpredetermined processes in a layered manner in the photolithographystep; and an interface unit 112, provided adjacent to the processingstation 110, for delivering the wafer 104 to an exposure device (notshown).

A cassette support stand 114 is provided at the cassette station 102;the cassette support stand 114 may freely carry a plurality of cassettes106 in a row in the X direction (vertically, in FIG. 1). The cassettestation 102 is provided with a wafer transporter 116 able to move on thetransport path 118 in the X direction. The wafer transporter 116 mayalso move freely in the wafer array direction (Z direction;perpendicular) of the wafers 104 housed in the cassette 106 and canselectively access the wafer 104 vertically arrayed in the cassette 106.The wafer transporter 116 may rotate around an axis (8 direction) in theparticular direction, and may also access the inspection station'stransfer unit 120.

Disposed at the cassette station 102 side of inspection station 108 isthe transfer unit 120 for transferring the wafer 104 from the cassettestation 102. A carrying unit 122 for carrying the wafer 104 may beprovided in the transfer unit 120. A wafer transporter 124 able to moveon a transport path 126 in the X direction may be provided at thepositive X direction side (upward in FIG. 1) of the inspection station108. The wafer transporter 124 also may move vertically and rotatefreely in the θ direction, and may also access the transfer unit 120 andeach processing device in a processing device group 130 at theprocessing station 110 side.

A processing station 110 adjacent to the inspection station 108 isprovided with a plurality of processing devices disposed in stages, suchas five processing device groups 128-132. The first processing devicegroup 128 and the second processing device group 129 are disposed insequence from the inspection station 108 side, at the negative Xdirection side (downward in FIG. 1) of the processing station 110. Thethird processing device group 130, fourth processing device group 131,and fifth processing device group 132 are disposed in sequence from theinspection station 108 side, at the positive X direction side (upward inFIG. 1) of the processing station 110. A first transport device 134 isprovided between the third processing device group 130 and the fourthprocessing device group 131. The first transport device 134 maytransport the wafer 104 to access each device in the first processingdevice group 128, third processing device group 130, and fourthprocessing device group 131. A second transport device 136 transportsthe wafer 104 and selectively accesses the second processing devicegroup 129, fourth processing device group 131, and fifth processingdevice group, 132.

With further reference to FIG. 2, the first processing device group 128stacks liquid processing devices that supply a predetermined liquidspin-on material to the wafer 104 and process it. Devices such as spincoating devices 140, 141, and 142, which may apply a photoresistsolution to the wafer 104 and form a photoresist film, and bottomcoating devices 143 and 144, which form an anti-reflection film thatprevents light reflection during exposure processing, may be arranged infive levels in sequence from the bottom. The second processing devicegroup 129 stacks liquid processing devices such as developing devices150-154, which supply developer (i.e. developer liquid) to the wafer 104and develop it, in five levels in sequence from the bottom. Also,terminal chambers 160 and 161 are provided at the lowest stages of thefirst processing device group 128 and the second processing device group129 in order to supply processing liquids to the liquid processingdevices in the processing device groups 128 and 129.

Also, as shown in FIG. 3, for example, the third processing device group130 stacks temperature regulation device 170, transition device 171 fortransfer of the wafer 104, high precision temperature regulation devices172-174, which regulate the temperature of the wafer 104 under highprecision temperature management, and high temperature heating devices175-178, which heat the wafer 104 to high temperature, in nine levels insequence from the bottom.

The fourth processing device group 131 stacks a high precisiontemperature regulation device 180, pre-baking devices 181-184 forheating the wafer 104 after photoresist coating processing, andpost-baking devices 185-189, which heat the wafer 104 after developing,in ten levels in sequence from the bottom. Each of the pre-bakingdevices 181-184 and post-baking devices 185-189 includes at least onehot plate wafer holder (not shown) for elevating the temperature of thewafer 104 and the layer on the wafer 104.

The fifth processing device group 132 stacks a plurality of heatingdevices that heat the wafer W, such as high precision temperatureregulation devices 190-193, and post-exposure baking devices 194-199 inten levels in sequence from the bottom.

A plurality of processing devices may be disposed at the positive Xdirection side of the first transport device 134 as shown in FIG. 1.Adhesion devices 200 and 202 for making the wafer 104 hydrophobic andheating devices 204 and 206 for heating the wafer 104 are stacked infour levels in sequence from the bottom, as shown in FIG. 5, forexample. A peripheral exposure device 208 for selectively exposing onlythe edge of the wafer 104 may be disposed at the positive X directionside of the second transport device 136 as shown in FIG. 1.

Provided in the interface unit 112 are a wafer transporter 210 thatmoves on a transport path 212 extending in the X direction as shown inFIG. 1 and a buffer cassette 214. The wafer transporter 210 can move inthe Z direction and can rotate in the θ direction; and can transport thewafer 104 and access the exposure device (not shown) adjacent to theinterface unit 112 and the buffer cassette 214 and the fifth processingdevice group 132.

FIG. 5 shows a flowchart of an exemplary embodiment of aphotolithography process 400 comprising steps for mitigating collapse ofphotoresist line patterns. FIG. 4 depicts the same process outlined inthe flowchart of FIG. 5 starting with rinsing step 450, and ending withthe gap-fill layer removal step 480. In step 410, the substrate (e.g. asemiconductor wafer, LCD panel, or photovoltaic device panel) is coatedwith a layer of photoresist in e.g. spin coating devices 140, 141, and142, of coating/developing system 100, of FIGS. 1-3. In step 420, thephotoresist layer is exposed to light to impart a latent image linepattern therein. This step is performed in an exposure device (not shownin FIGS. 1-3). In step 430, the substrate is exposed to an elevatedtemperature in a post-exposure bake step, which serves multiple purposesin photoresist processing. First, the elevated temperature of the bakedrives the diffusion of the photoproducts (i.e. photo-acid) in thephotoresist. A small amount of diffusion may be useful in minimizing theeffects of standing waves, which are the periodic variations in exposuredose throughout the depth of the photoresist layer that result frominterference of incident and reflected radiation during exposure.Another main purpose of the bake is to drive an acid-catalyzed reactionthat alters polymer solubility in many chemically amplified resists.Post-exposure bake also plays a role in removing solvent from thesubstrate surface. In step 440, the substrate is transferred to adeveloping device, such as for example, one of developing devices150-154 of coating/developing system 100, of FIGS. 1-3. In thedeveloping device, developer (i.e. developer liquid) is dispensed ontothe substrate to activate the photoproducts in the photoresist, andthereby develop portions of the photoresist, leaving a developedphotoresist line pattern on the substrate.

With further reference to the flowchart of FIG. 5, and the schematic ofFIG. 4, in step 450, excess developer is rinsed from the developedphotoresist line pattern 310, and the substrate 300 by dispensing rinseliquid 330, such as deionized water, from a rinse liquid nozzle 320. Therinse liquid 330 may contain various additives, such as surfactants toreduce the surface tension of the rinse liquid 330, and to aid indisplacing the developer. In step 460, in order to prevent photoresistline pattern 310 from collapsing during the step of drying rinse liquid330 from the substrate, a gap-fill treatment liquid 350 is dispensedonto the photoresist line pattern 310, and substrate 300, to fullydisplace the rinse liquid 330. In step 470, excess gap-fill treatmentliquid 350 is spun off the substrate 300 and photoresist line pattern310, typically by spinning (i.e. rotating) the substrate 300 within oneof the developing devices 150-154 of coating/developing system 100, ofFIGS. 1-3. Once excess gap-fill treatment liquid is removed, theremaining amount is allowed to dry and form a solid gap-fill layer 360,which fills the inter-line spaces of the photoresist line pattern 310,preventing collapse thereof during drying. Finally, in step 480, thegap-fill material layer is removed from the substrate 300, therebyexposing the photoresist line pattern 310. The step 480 of removing thegap-fill layer 360 can be performed in a multitude of ways, e.g. using adry etch process in an etch tool, or using a depolymerizing agent, suchas heat, electromagnetic radiation, or a chemical catalyst to causedepolymerization of the gap-fill polymer material. Duringdepolymerization, volatile monomer compounds are formed and evolved fromthe surface of the gap-fill layer material, and eventually the entiregap-fill layer 360 is removed from the photoresist line pattern 310. Theprocess of depolymerization will be discussed in greater detail later.It is important to note that, unlike during conventional drying of rinseliquid 330, the depolymerization, volatilization, and evolution of thesolidified gap-fill layer 360 during step 480 does not give rise tocapillary forces, and therefore the risk of photoresist line patterncollapse is mitigated.

The gap-fill treatment liquid 350 and solidified gap-fill layer materialhave to satisfy a number of requirements to be suitable for use in thephotolithography process 400. First, the gap-fill treatment liquid 350has to comprise a polymer that is soluble in a solvent so it can be spunonto the substrate 300 inside the developing device, such as one ofdeveloping devices 150-154 of coating/developing system 100, of FIGS.1-3. For compatibility with the developer and rinse liquids used withinthe same developing device, it is preferable that the polymer bewater-soluble (i.e. employ water as a solvent). However, it is alsopossible to use a polymer which is not water-soluble, but utilizes asolvent such as e.g. an alcohol, which is chemically compatible withother liquids used in the developing device. The solvent is evolved fromthe gap-fill treatment liquid 350 during the drying step 470 to form thegap-fill layer 360. The gap-fill treatment liquid also needs to beself-planarizing during the spin-off and drying step 470, it has to havegood pattern wetting and filling properties so as to not leave voidsbetween the photoresist pattern lines, and it also has to completelydisplace the rinse liquid and be chemically compatible with it.

Second, the polymer of which the solidified gap-fill layer 360 iscomprised has to be readily removable. If a plasma etch process is usedfor removal of gap-fill layer 360, it is important that the gap-fillpolymer plasma etch process have good selectivity with respect tophotoresist and other materials that are exposed to the plasma etchprocess chemistry. In other embodiments, the gap-fill layer can becaused to depolymerize (i.e. unzip) into volatile monomer compoundswhich are readily evolved from the surface of gap-fill layer 360 andpumped away, to expose the photoresist line pattern 310. If adepolymerization removal process is used, then the polymer needs toreadily respond to the application of a depolymerization agent, such asheat, electromagnetic radiation, or a chemical catalyst, by breaking-upinto volatile monomer compounds.

In one exemplary embodiment, a polymeric compound can be depolymerizedby elevating the temperature of the substrate 300 and all layersdeposited thereupon, in a heating device such as high temperatureheating devices 175-178 of coating/developing system 100, of FIGS. 1-3.Other devices, such as pre-baking devices 181-184 and post-bakingdevices 185-189 of coating/developing system 100, of FIGS. 1-3, can alsobe used to elevate the substrate temperature to depolymerize thegap-fill layer material. An exemplary schematic of a heating device 700is shown in FIG. 8. The heating device 700 comprises an enclosure 710,inside which a hot plate 720 is disposed and configured to receive asubstrate 730, with a gap-fill layer 360 formed thereon. Heatersembedded in the hot plate 720 are used to elevate the temperature ofsubstrate 730 and the gap-fill layer 360. Optional lift pins 740 can beused to elevate the substrate 730 from the hot plate 720 during theheating step, to improve heating uniformity. The temperature to whichthe substrate 300 and gap-fill layer 360 have to be heated depends onthe gap-fill material depolymerization (i.e. unzip) temperature, theresistance of the photoresist and other surrounding materials toelevated temperatures, etc. In general, the temperature used can varyfrom about 10° C. to 20° C. below the gap-fill material depolymerizationtemperature, to almost as high as the temperature at which photoresistis damaged. With the above in mind, and for typical gap-fill polymersand photoresist materials, practical depolymerization temperatures willvary from 30° C. to 200° C., and more preferably from 50° C. to 150° C.

In another exemplary embodiment, a polymeric compound can bedepolymerized by illumination with electromagnetic radiation. This canbe achieved in a module of coating/developing system 100, of FIGS. 1-3(not shown), in which a lamp, laser, or similar device, are used as asource of electromagnetic radiation which causes the gap-fill materialto depolymerize. FIG. 9 shows an exemplary schematic of an illuminationdevice 800, to be used for illumination of gap-fill layer 360 withelectromagnetic radiation. Illumination device 800 comprises anenclosure 810, inside which a pedestal 820 is disposed to receive asubstrate 830 with a gap-fill layer 360 deposited thereupon. Optionallift pins 840 can be used to elevate the substrate during illuminationto reduce heat loss from the substrate 830 during illumination. A lightsource 850 is used to generate electromagnetic radiation forillumination of the gap-fill layer 360. The light source 850 can be alamp, laser, or a combination of two or more thereof. In one exemplaryembodiment, an ultraviolet lamp can be used as light source 850, toilluminate the gap-fill layer 360 with ultraviolet light of sufficientlyhigh photon energy to initiate polymer bond breakage, anddepolymerization. In another embodiment, a visible light or infraredlamp can be used as light source 850, the latter causingdepolymerization primarily via a heating effect. In yet anotherembodiment, a laser, such as a visible light or infrared laser, can beused as light source 850. The laser comprising the light source 850 canbe operated in continuous or pulsed (i.e. spike illumination) mode, thelatter being particularly suitable for gap-fill layer illuminationbecause an exact dose of electromagnetic radiation can be delivered tothe gap-fill layer 360 without causing undue heating of underlyinglayers and the substrate, which allows safe processing of devices with arelatively low thermal budget. Typical pulse (i.e. spike) times canrange from 1 ms to 100 ms, or more preferably from 1 ms to 10 ms. Pulsedillumination is also possible with a lamp used as light source 850. Anoptical waveguide 860 guides the electromagnetic radiation from lightsource 850 to the beam shaping optics 870. The beam shaping optics 870ensure that the electromagnetic radiation from light source 850 isevenly distributed over the substrate 830 and gap-fill layer 360. Thiseven illumination can be achieved in a number of ways. In oneembodiment, a system of fixed optics (e.g. mirrors, lenses, andwaveguides) can be employed to spread the electromagnetic radiation intolight beam 880, reaching all points on the substrate 830 and gap-filllayer 360, simultaneously. Alternatively, beam shaping optics 870 cancomprise an optical scanner element that directs the light beam 880 ontojust a portion of substrate 830 and gap-fill layer 360, scanning thelight beam over time to process other portions of substrate 830.Alternatively yet, fixed beam shaping optics 870 can be configured toilluminate only a portion of substrate 830 and gap-fill layer 360, andthe pedestal 820 can be mounted on a translation and/or rotation stage(not shown), allowing all portions of the substrate 830 and gap-filllayer 360 to be illuminated by scanning the pedestal 820 with asubstrate 830 under the light beam 880. In embodiments where pulsed(i.e. spike) illumination is used, the pulse illumination can optionallybe synchronized with the scanning of light beam 880 or the scanning ofpedestal 820, via a controller (not shown), to evenly illuminate theentire gap-fill layer 360.

In yet another exemplary embodiment, a chemical catalyst compound can beapplied to the gap-fill layer 360 which will initiate gap-fill materialpolymer bond breakage, and cause it to depolymerize and evolve.Typically, an acid catalyst would be used to initiate polymer bondbreakage. The advantage of this embodiment is that the gap-fill layerremoval step 480 can be performed in the developing device, i.e. withouthaving to transport the substrate to another module of thecoating/developing system.

FIG. 7 shows an embodiment of a developing device, such as one ofdeveloping devices 150-154 of coating/developing system 100, of FIGS.1-3, suitable for performing portions of the photolithography process400 outlined in FIGS. 4 and 5. Developing device 500 comprises a cup 510inside which a substrate chuck or support structure 530 is configured toreceive and clamp a substrate 550 thereupon. The substrate chuck 530 hasa first end 532 configured to clamp the substrate, typically using avacuum or electrostatic force, and a second end 535 attached to aspindle 540 of a drive motor (not shown) which is used to spin thesubstrate during dispensing and spin-off steps. Excess dispensed liquidis fed outside the cup 510 via liquid ports 520, and vapors arepumped-out via vapor ports 522. During each dispensing step performed inthe developing device 500, a layer 560 of the dispensed liquid is formedon the top surface of substrate 550.

With further reference to FIG. 7, the developing device 500 comprises atleast four nozzles 620, 650, 680, and 695 used to dispense developer,rinse liquid, gap-fill treatment liquid, and catalyst liquidrespectively. In some embodiments, multiple nozzles or arrays of nozzlescan be used to dispense a liquid, instead of single nozzles 620, 650,680, and 695. Also, the nozzles or nozzle arrays can be stationary ormovable to facilitate uniform dispensing of liquids onto the substratesurface. Nozzles 620, 650, 680, and 695 are connected to developersource 600, rinse liquid source 630, gap-fill treatment liquid source660, and catalyst liquid source 690, via tubing runs 610, 640, 670, and692, respectively. In performing the steps of photolithography process400 of FIGS. 4 and 5, the nozzles 620, 650, 680, and 695 are opened, andsources 600, 630, 660, and 690 are activated to dispense the developer,rinse liquid, gap-fill treatment liquid, or catalyst liquid during steps440, 450, 460, and 480, respectively, of photolithography process 400depicted in FIG. 5. The addition of a catalyst nozzle 695 to thedeveloping device 500 allows catalyst-initiated depolymerization of thegap-fill layer 360 to occur immediately after drying step 470, andwithout the need for removing the substrate 550 from developing device500.

In another alternative embodiment, a developing device 500 can beequipped with a light source and beam shaping optics, such as lightsource 850 and beam shaping optics 870, of illumination device 800, toallow illumination of substrate 550 within the developing device 500.This embodiment does not require that separate illumination devices,such as illumination device 800, be installed inside coating/developingsystem 100, of FIGS. 1-3.

FIG. 6 shows a number of polymer compounds that can be used as agap-fill treatment liquid and that may solidify into a suitable gap-filllayer material. In general, most polymer materials have very lowdepolymerization (i.e. ceiling) temperatures, i.e. below typical ambienttemperatures, so they are typically end-capped to increase theirstability. The process of depolymerizing via application of one of theabove depolymerizing agents (heat, electromagnetic radiation, or acatalyst) starts by the agent causing bond breakage “events”, afterwhich the polymer fully “unzips”.

In one exemplary embodiment, poly(methyl glyoxylate) is used as agap-fill polymer. This compound is a polymeric salt of the poly(methylglyoxylic acid), wherein the ion can be e.g. a sodium ion Na⁺, or anammonium ion NH₄ ⁺. In a preferred embodiment, the ammonium salt is usedbecause upon application of heat to this polymeric salt, two usefulchemical changes occur. First, the ammonium ion NH₄ ⁺ will give up ahydrogen atom to the poly(methyl glyoxylate), and become ammonia NH₃,which readily evolves from the polymer. And second, because the polymerhas oxygen in its backbone, it is unstable, and will “unzip” if one ofthe oxygen bonds are broken due to action of a depolymerization agent,such as heat, with the resulting monomer compounds also evolving fromthe polymer. Other compounds listed in FIG. 6 have similardepolymerization mechanisms, some of which are described in theliterature, e.g. Brachais et al., “In Vitro Degradation of poly(methylglyoxylate) in Water”, Polymer, vol. 39, pp. 883-890, 1998; Tsuda etal., “Acid-catalyzed Degradation Mechanism of poly(phtalaldehyde):Unzipping Reaction of Chemical Amplification Resist”, Journal of PolymerScience: Part A, Polymer Chemistry, vol. 35, pp. 77-89, 1997; andBelloncle et al., “Synthesis and Degradation of poly(ethyl glyoxylate)”,in “Polymer Degradation and Performance”, chap. 4, pp. 41-51, ACSSymposium Series, ACS 2009, the contents of all of which areincorporated herein in their entirety. Additionally, U.S. Pat. No.6,576,714 entitled “Production Process for Glyoxylic Acid (Salt)-BasedPolymer”, to Saeki et al., provides useful background information aboutthe stability, end-capping, production, etc., of polymeric salts of theglyoxylic acid, and is also incorporated herein in its entirety.

With further reference to FIG. 6, the polymer compoundpoly(phtalaldehyde) is a polymer of monomer phtalaldehyde, which monomeris also commonly known as o-phtalaldehyde or ortho-phtalaldehyde.

In another embodiment, a gap-fill treatment liquid 350 can be used, withor without a solvent, which would react with the rinse liquid, e.g.deionized water present at the substrate, to form an in-situ gel thatfills inter-line spaces in the photoresist line pattern 310. The gelwould be removed using similar process steps to those described above,e.g. using plasma etch, or depolymerized the gel by applying heat,electromagnetic radiation, or a chemical catalyst.

Reference throughout this specification to “one embodiment” or “anembodiment” means that a particular feature, structure, material, orcharacteristic described in connection with the embodiment is includedin at least one embodiment of the invention, but do not denote that theyare present in every embodiment. Thus, the appearances of the phrases“in one embodiment” or “in an embodiment” in various places throughoutthis specification are not necessarily referring to the same embodimentof the invention. Furthermore, the particular features, structures,materials, or characteristics may be combined in any suitable manner inone or more embodiments.

Various operations will be described as multiple discrete operations inturn, in a manner that is most helpful in understanding the invention.However, the order of description should not be construed as to implythat these operations are necessarily order dependent. In particular,these operations need not be performed in the order of presentation.Operations described may be performed in a different order than thedescribed embodiment. Various additional operations may be performedand/or described operations may be omitted in additional embodiments.

Persons skilled in the relevant art can appreciate that manymodifications and variations are possible in light of the aboveteaching. Persons skilled in the art will recognize various equivalentcombinations and substitutions for various components shown in thefigures. It is therefore intended that the scope of the invention belimited not by this detailed description, but rather by the claimsappended hereto.

What is claimed is:
 1. A method of patterning a substrate, comprising:forming a layer of radiation-sensitive material on the substrate;performing a patterned exposure of the layer of radiation-sensitivematerial; performing a post-exposure bake of the layer ofradiation-sensitive material; developing the layer ofradiation-sensitive material to form a radiation sensitive materialpattern; rinsing the radiation-sensitive material pattern with a rinseliquid; dispensing gap-fill treatment liquid on the radiation-sensitivematerial pattern to displace the rinse liquid; spinning the substrate toremove excess gap-fill treatment liquid and allow the remaining gap-filltreatment liquid to dry, thereby forming a gap-fill material layer whichprevents collapse of the radiation-sensitive material pattern; andremoving the gap-fill material layer from the radiation-sensitivematerial pattern, wherein the step removing the gap-fill material layercomprises exposing the gap-fill material layer to electromagneticradiation, heating the gap-fill material layer by a heat source,exposing the gap-fill material layer to a catalyst, etching the gap-fillmaterial layer, or a combination of two or more thereof, and wherein thegap-fill treatment liquid comprises at least one polymer compound fromthe group consisting of poly(phtalaldehyde), poly(succinaldehyde),poly(allyl alcohol), poly(glyoxylic acid), poly(methyl glyoxylic acid),a polymeric salt of poly(methyl glyoxylic acid), poly(ethyl glyoxylicacid), a polymeric salt of poly(ethyl glyoxylic acid), poly(methylglyoxylate), and poly(ethyl glyoxylate).
 2. A chemical composition of agap-fill treatment liquid comprising: at least one polymer compound fromthe group consisting of poly(phtalaldehyde), poly(succinaldehyde),poly(allyl alcohol), poly(glyoxylic acid), poly(methyl glyoxylic acid),a polymeric salt of poly(methyl glyoxylic acid), poly(ethyl glyoxylicacid), a polymeric salt of poly(ethyl glyoxylic acid), poly(methylglyoxylate), and poly(ethyl glyoxylate), wherein the gap-fill treatmentliquid depolymerizes into volatile compounds on exposure to at least onedepolymerizing agent from the group consisting of heat, electromagneticradiation, and a catalyst.
 3. The chemical composition of claim 2,wherein the electromagnetic radiation comprises infrared radiation. 4.The chemical composition of claim 2, wherein the electromagneticradiation comprises visible light radiation.
 5. The chemical compositionof claim 2, wherein the electromagnetic radiation comprises ultravioletradiation.
 6. The chemical composition of claim 2, wherein the catalystcomprises an acid.
 7. The chemical composition of claim 2, wherein theexposure of the gap-fill treatment liquid to heat comprises heating thegap-fill treatment liquid to a temperature between 30° C. and 200° C. 8.The chemical composition of claim 2, wherein the exposure of thegap-fill treatment liquid to heat comprises heating the gap-filltreatment liquid to a temperature between 50° C. and 150° C.
 9. Thechemical composition of claim 2, wherein the gap-fill treatment liquidcomprises a solvent.
 10. The chemical composition of claim 9, whereinthe solvent comprises water.
 11. The chemical composition of claim 9,wherein the solvent comprises an alcohol.
 12. The chemical compositionof claim 2, wherein the polymeric salt of poly(methyl glyoxylic acid) isan ammonium salt of poly(methyl glyoxylic acid).
 13. The chemicalcomposition of claim 2, wherein the polymeric salt of poly(methylglyoxylic acid) is a sodium salt of poly(methyl glyoxylic acid).
 14. Thechemical composition of claim 2, wherein the polymeric salt ofpoly(ethyl glyoxylic acid) is an ammonium salt of poly(ethyl glyoxylicacid).
 15. The chemical composition of claim 2, wherein the polymericsalt of poly(ethyl glyoxylic acid) is a sodium salt of poly(ethylglyoxylic acid).